CN101001886B - Redox curing-type nonaqueous curable composition - Google Patents
Redox curing-type nonaqueous curable composition Download PDFInfo
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- CN101001886B CN101001886B CN2005800270207A CN200580027020A CN101001886B CN 101001886 B CN101001886 B CN 101001886B CN 2005800270207 A CN2005800270207 A CN 2005800270207A CN 200580027020 A CN200580027020 A CN 200580027020A CN 101001886 B CN101001886 B CN 101001886B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
Abstract
A nonaqueous curable composition comprising a liquid radical polymerizable monomer (a), an organic peroxide (b), and a powdery water-soluble reducing compound (c), the powdery water-soluble reducing compound (c) being dispersed in the liquid radical polymerizable monomer (a). The nonaqueous curable composition can ensure a time necessary for bonding operation and, at the same time, can provide excellent bonding strength to a wet substance, especially an organism hard tissue such as dentin and, thus, is industrially very valuable.
Description
Technical field
The present invention relates to redox curing-type nonaqueous curable composition, more particularly, relate to by contacting the redox curing-type nonaqueous curable composition that promotes curing reaction with the wetting body that contains moisture (hereinafter referred is " wetting body ").
Background technology
Wetting body for example uses adhesives in the repairing and treating of organism such as tooth, bone sclerous tissues.As the adhesives that is used for wetting body, widespread use contains the resene solidification compound of free radical polymerization monomer, polymerization starter etc.
For the resene solidification compound,, 2 kinds of motions were arranged substantially in the past in order to improve to wetting body, the particularly cementability of organism sclerous tissues.That is, relate to and be intended to improve the motion (with reference to following patent documentation 1～3) that contains the free radical polymerization monomer of acidic-group with chemistry-physical interaction as matrix such as the tooth of adhering object, bones; And relate to and be intended to make the solidification compound that contains free radical polymerization monomer in organism sclerous tissues, to carry out the motion (with reference to following patent documentation 4～6) of the polymerization starter of polymerizing curable effectively with acidic-group.
But, on wetting body, during the solidification compound of adhering resin class, hindering owing to be present in the caused curing of the oxygen of bonding interface, the situation that can not obtain sufficient adhesion strength is a lot.This curing hinders obvious especially when dentine that solidification compound is adhered to the tooth that contains a large amount of oxygen or bone.
Therefore, hinder, promote polymerization curing reaction, proposed to use the reductionoxidation polymerization initiator that contains catalyzer (oxygenant) and promotor (reductive agent) in order to suppress the curing that oxygen that wetting body contains causes.As promotor, the reductibility compound that particularly contains sulphur obtains paying close attention to (with reference to following patent documentation 7～10).
For example, in the following patent documentation 9, proposed to contain the redox curing type water system Polymerizable composition of the 1st dose and the 2nd dose, described the 1st dose of aqueous ethanol, sulphite and tertiary amine etc.; Described the 2nd dose contains free-radical polymerised liquid monomer and catalyzer.In addition, in the following patent documentation 10, proposed to contain the redox curing type water system tooth section bonding composition of the 1st dose, the 2nd dose and the 3rd dose, described the 1st dose contains polymerizability phosphorus compound, polymerizing catalyst and thinner; Described the 2nd dose contains water-based ethanol, sulphur compound and tertiary amine; Described the 3rd dose contains water-based ethanol and FeCl
3Deng soluble metallic salt.The redox curing type water system solidification compound of these subpackage types is that each agent with subpackage is mixed and made into 1 dose and in using.
Patent documentation 1: the spy opens clear 53-67740 communique
Patent documentation 2: the spy opens clear 54-11149 communique
Patent documentation 3: the spy opens clear 58-21687 communique
Patent documentation 4: the spy opens clear 45-29195 communique
Patent documentation 5: the spy opens clear 53-39331 communique
Patent documentation 6: the spy opens clear 62-175410 communique
Patent documentation 7: the spy opens flat 06-40835 communique
Patent documentation 8: the spy opens flat 06-40838 communique
Patent documentation 9: the spy opens clear 57-168903 communique
Patent documentation 10: the spy opens clear 58-125710 communique
Summary of the invention
For the existing redox curing type water system solidification compound described in patent documentation 9 or 10, if raising cooperate promotor such as a large amount of sulphite, tertiary amine with the bonding strength of wetting body, then redox reaction is carried out fast, and usable time greatly shortens, and is unsuitable for practicality.On the other hand, if guarantee the needed time of bonding operation and make the use level of promotor to be less amount, then solidify insufficiently, reduce with the bonding strength of wetting body.
Therefore, the inventor furthers investigate for the above-mentioned mutual problem that solves existing redox curing type water system solidification compound and had, found that, it is a kind of with the bonding interface portion of wetting body rather than in the inner phenomenon that takes place of solidification compound being hindered by the caused polymerization of oxygen, therefore if only optionally promote the redox reaction of the bonding interface portion that the generation polymerization hinders, then usable time can greatly not shorten, and can improve with the bonding strength of wetting body.
The present invention is based on above-mentioned discovery and finishes, and its purpose is the time that can guarantee that bonding operation is required is provided, and to wetting body, and particularly organism sclerous tissues such as dentine shows the redox curing type solidification compound of excellent bonding strength.
Being used to reach the redox curing-type nonaqueous curable composition that the invention of scheme 1 record of above-mentioned purpose relates to is the redox curing-type nonaqueous curable composition that contains liquid free radical polymerization monomer (a), organo-peroxide (b) and powdery, water-soluble reductibility compound (c), and its water-soluble reductibility compound of dispersed powders shape (c) in liquid free radical polymerization monomer (a) forms.
The invention of scheme 2 record is that the powdery, water-soluble reductibility compound (c) in the invention of scheme 1 record is restricted to the sulphite powder.
The invention of scheme 3 records is that the redox curing-type nonaqueous curable composition that the invention of scheme 1 record relates to is restricted to respect to liquid free radical polymerization monomer (a) 100 weight parts, contains organo-peroxide (b) 0.05～10 weight part and powdery, water-soluble reductibility compound (c) 0.01～15 weight part.
The invention of scheme 4 record is that the redox curing-type nonaqueous curable composition of scheme 1 record is restricted to and is packetized into the 1st dose and the 2nd dose, and described the 1st dose contains liquid free radical polymerization monomer (a) and organo-peroxide (b); Described the 2nd dose contains liquid free radical polymerization monomer (a) and powdery, water-soluble reductibility compound (c).
The invention of scheme 5 record is that the powdery, water-soluble reductibility compound (c) in the invention of scheme 4 records is restricted to the sulphite powder.
The invention of scheme 6 record is that the redox curing-type nonaqueous curable composition of scheme 4 records is restricted to following subpackage: the 1st dose contains organo-peroxide (b) 0.1～50 weight part with respect to liquid free radical polymerization monomer (a) 100 weight parts, the 2nd dose contains powdery, water-soluble reductibility compound (c) 0.1～50 weight part with respect to liquid free radical polymerization monomer (a) 100 weight parts, and the weight ratio of the 1st dose and the 2nd dose is 1: 10～10: 1.
Hereinafter, the redox curing-type nonaqueous curable composition of sometimes scheme 1～6 being put down in writing is referred to as the present composition.
The invention of scheme 7 record is that the purposes of the redox curing-type nonaqueous curable composition that relates to of the invention of any record in the scheme 1～6 is restricted to organism sclerous tissues caking agent.
By the present invention, provide the time that can guarantee that bonding operation is required, and to wetting body, particularly organism sclerous tissues such as dentine shows the redox curing-type nonaqueous curable composition of excellent bonding strength.Its reason is presumed as follows.
Because the caused polymerization obstruction of oxygen takes place the bonding interface portion at redox curing type solidification compound and wetting body, the polymerization-curable of bonding interface portion is lower than inside.When utilizing existing water system solidification compound, if improve bonding interface portion polymerization-curable and in the water system solidification compound a large amount of water-soluble reductibility compound of dissolving, then owing to also improved the polymerization-curable of the inside that there is no need to improve polymerization-curable simultaneously, therefore all shortenings set time of composition are difficult to the time of guaranteeing that bonding operation is required.In addition, when utilizing existing water system solidification compound, if guarantee the time that bonding operation is required and reduce the amount that is dissolved in the water-soluble reductibility compound in the water system solidification compound, then be difficult to obtain with wetting body, particularly contain the sufficient cementability of the organism sclerous tissueses such as dentine of a large amount of oxygen.Relative therewith, the powdery, water-soluble reductibility compound (c) that is present in the bonding interface portion of the present composition is dissolved in the water on wetting body surface.The powdery, water-soluble reductibility compound (c) that is dissolved in the water and be dissolved in the frequency height that the organo-peroxide (b) in the liquid free radical polymerization monomer (a) mutually meets with molecularity.That is, easily carry out redox reaction as the free radical formation reaction.On the other hand, because being present in the powdery, water-soluble reductibility compound (c) of present composition inside is that the frequency of meeting with molecularity with the organo-peroxide (b) that is dissolved in the liquid free radical polymerization monomer (a) is low in liquid free radical polymerization monomer (a) undissolved Powdered (solid).Thereby, only optionally improved the polymerization-curable of the bonding interface portion that is necessary to improve polymerization-curable.More than wetting body is shown the reason of excellent bonding strength for the present composition.In addition, ratio set time of the present composition is not with dispersion state but contains the length of the existing water system solidification compound of the powdery, water-soluble reductibility compound (c) of amount together of the same race with dissolved state, this be because: because the powdery, water-soluble reductibility compound (c) that is present in present composition inside exists with the state of powder (solid), so the frequency of meeting with molecularity with organo-peroxide (b) is low, so all polymerizing curable speed of composition is so not fast.
Embodiment
Liquid free radical polymerization monomer (a) carries out Raolical polymerizable and the polymerizable monomer of high molecular by the reductionoxidation polymerization initiator.Be noted that among the present invention that " liquid state " is meant in room temperature (25 ℃) and is the state of liquid.The free radical polymerization monomer that constitutes the liquid free radical polymerization monomer (a) among the present invention is not limited to a kind, can be for more than 2 kind or 2 kinds, and still employed free radical polymerization monomer integral body must be liquid in room temperature.That is, when the free radical polymerization monomer that constitutes liquid free radical polymerization monomer (a) only was a kind, this free radical polymerization monomer was necessary for liquid state in room temperature.In addition, the free radical polymerization monomer that constitutes liquid free radical polymerization monomer (a) is more than 2 kinds or 2 kinds the time, and their mixture is necessary for liquid state in room temperature.Therefore, liquid free radical polymerization monomer (a) is during by the constituting of the free radical polymerization monomer more than 2 kinds or 2 kinds, as long as their combination at room temperature forms liquid mixture, then both can be to be the combination between the liquid free radical polymerization monomer under the room temperature, also can be for being the combination of solid-state free radical polymerization monomer under the room temperature under liquid free radical polymerization monomer and the room temperature.As the free radical polymerization monomer that can constitute liquid free radical polymerization monomer (a), can enumerate the ester class of carboxylic acids such as alpha-cyanoacrylate, (methyl) vinylformic acid, alpha-halogen vinylformic acid, Ba Dousuan, styracin, Sorbic Acid, toxilic acid, methylene-succinic acid; (methyl) acrylamide and derivative thereof; Vinyl ester; Vinyl ethers; List-N-ethenyl derivatives; Styrene derivatives.Wherein, preferred (methyl) acrylate.
The object lesson of free radical polymerization monomer that can constitute liquid free radical polymerization monomer (a) is as described below.The monomer that will have the two keys of 1 alkene is designated as monofunctional monomer, and the monomer that will have the two keys of 2 alkene is designated as two functional monomers, and the monomer that will have 3 or 3 the two keys of above alkene is designated as trifunctional or the above monomer of trifunctional.
Monofunctional monomer:
(methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) benzyl acrylate, (methyl) lauryl acrylate, 2,3-dibromopropyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, 1,3-dihydroxypropyl (methyl) acrylate, 2,3-dihydroxypropyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylamide, the 3-methacryloxypropyl trimethoxy silane, 11-methacryloxy undecyl Trimethoxy silane, (methyl) acrylamide
Two functional monomers:
Ethylene glycol bisthioglycolate (methyl) acrylate; triethylene glycol two (methyl) acrylate; propylene glycol two (methyl) acrylate; polyoxyethylene glycol two (methyl) acrylate (number of oxyethylene group is more than 9 or 9); neopentyl glycol two (methyl) acrylate; 1; 6-hexylene glycol two (methyl) acrylate; 1; 10-decanediol two (methyl) acrylate; Dipentaerythritol two (methyl) acrylate; dihydroxyphenyl propane diglycidyl (methyl) acrylate; 2; two [4-(methyl) acryloxy ethoxyl phenenyl] propane of 2-; 2; two [4-(methyl) the acryloxy polyethoxye phenyl] propane of 2-; 2; two [4-[3-(methyl) acryloxy-2-hydroxyl propoxy-] phenyl of 2-] propane; 1; two [3-(methyl) acryloxy-2-hydroxyl propoxy-] ethane of 2-; tetramethylolmethane two (methyl) acrylate; 1; two (3-methacryloxy-2-hydroxyl propoxy-) ethane of 2-; [2; 2; 4-tri-methyl hexamethylene two (2-formamyl oxygen base ethyl)] dimethacrylate; 1,3-two (methyl) acryloxy-2-hydroxy propane
The monomer that trifunctional or trifunctional are above:
Trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, N, N '-(2,2, the 4-tri-methyl hexamethylene) two [2-(amino carboxyl) propane-1, the 3-glycol] tetramethyl-acrylate, 1,7-two propylene acyloxy-2,2,6,6-tetrapropylene acyloxy methyl-4-oxygen base heptane.
Aspect the cementability that improves with wetting body, the preferred cooperation makes the part that can constitute the free radical polymerization monomer of liquid free radical polymerization monomer (a) with the polymerizable monomer conduct that contains acidic-group that is improved by the affinity of convered structure and have a decalcification.As the polymerizable monomer that contains acidic-group; can enumerate have at least 1 phosphate, acidic-group such as tetra-sodium base, carboxylic acid group, sulfonic group, and have the polymerizable monomer of polymerizable groups such as at least 1 acryl, methacryloyl, vinyl, styryl (can polymeric unsaturated group).The object lesson of this polymerizable monomer is as described below.
As the polymerizable monomer that contains phosphate, can enumerate 2-(methyl) acryloxy ethyl dihydrogen phosphoric acid ester, 3-(methyl) acryloxy propyl group dihydrogen phosphoric acid ester, 4-(methyl) acryloxy butyl dihydrogen phosphoric acid ester, 5-(methyl) acryloxy amyl group dihydrogen phosphoric acid ester, 6-(methyl) acryloxy hexyl dihydrogen phosphoric acid ester, 7-(methyl) acryloxy heptyl dihydrogen phosphoric acid ester, 8-(methyl) acryloxy octyl group dihydrogen phosphoric acid ester, 9-(methyl) acryloxy nonyl dihydrogen phosphoric acid ester, 10-(methyl) acryloxy decyl dihydrogen phosphoric acid ester, 11-(methyl) acryloxy undecyl dihydrogen phosphoric acid ester, 12-(methyl) acryloxy dodecyl dihydrogen phosphoric acid ester, 16-(methyl) acryloxy hexadecyl dihydrogen phosphoric acid ester, 20-(methyl) acryloxy eicosyl dihydrogen phosphoric acid ester, two [2-(methyl) acryloxy ethyl] hydrogen-phosphonate, two [4-(methyl) acryloxy butyl] hydrogen-phosphonate, two [6-(methyl) acryloxy hexyl] hydrogen-phosphonate, two [8-(methyl) acryloxy octyl group] hydrogen-phosphonate, two [9-(methyl) acryloxy nonyl] hydrogen-phosphonate, two [10-(methyl) acryloxy decyl] hydrogen-phosphonate, 1,3-two (methyl) acryloxy propyl group-2-dihydrogen phosphoric acid ester, 2-(methyl) acryloxy ethylphenyl hydrogen-phosphonate, 2-(methyl) acryloxy ethyl 2 '-the bromotrifluoromethane hydrogen-phosphonate, 2-(methyl) acryloxy ethyl-Phenylphosphine acid esters; (5-methacryloxy) amyl group-3-phosphono propionic ester, (6-methacryloxy) hexyl-3-phosphono propionic ester, (10-methacryloxy) decyl-3-phosphono propionic ester, (6-methacryloxy) hexyl-3-phosphinylidyne acetic acid ester, (10-methacryloxy) decyl-3-phosphinylidyne acetic acid ester, 2-methacryloxyethyl (4-p-methoxy-phenyl) hydrogen-phosphonate, 2-methacryloxypropyl (4-p-methoxy-phenyl) hydrogen-phosphonate; The spy opens clear 52-113089 communique, spy and opens clear 53-67740 communique, spy and open clear 53-69494 communique, spy and open clear 53-144939 communique, spy and open clear 58-128393 communique, spy and open the polymerizable monomer that contains phosphate enumerated in the clear 58-192891 communique and their chloride of acid.
As the polymerizable monomer that contains the tetra-sodium base, can enumerate two [2-(methyl) acryloxy ethyl] esters of tetra-sodium, two [4-(methyl) acryloxy butyl] esters of tetra-sodium, two [6-(methyl) acryloxy hexyl] esters of tetra-sodium, two [8-(methyl) acryloxy octyl group] esters of tetra-sodium, two [10-(methyl) acryloxy decyl] ester and their chloride of acid of tetra-sodium.
As the polymerizable monomer that contains the carboxylic acid group, can enumerate toxilic acid, methacrylic acid, 4-(methyl) acryloxy ethoxy carbonyl phthalic acid, 4-(methyl) acryloxy butoxy carbonyl phthalic acid, 4-(methyl) acryloxy hexyloxy carbonyl phthalic acid, 4-(methyl) acryloxy carbonyl octyloxy phthalic acid, 4-(methyl) acryloxy oxygen in last of the ten Heavenly stems base carbonyl phthalic acid and their acid anhydrides; The amino pentylformic acid of 5-(methyl) acryl, 6-(methyl) acryloxy-1; 1-hexmae dicarboxylic acid, 8-(methyl) acryloxy-1; 1-octane dicarboxylic acid, 10-(methyl) acryloxy-1; 1-decane dioctyl phthalate, 11-(methyl) acryloxy-1,1-undecane dioctyl phthalate and their chloride of acid.
As containing sulfonic polymerizable monomer, can enumerate 2-(methyl) acrylamide-2-methyl propane sulfonic acid, styrene sulfonic acid, 2-sulfoethyl (methyl) acrylate.Wherein, polymerizable monomer shown in the useization 1 with phosphate or thiophosphoric acid base, more preferably useization 2 or change shown in 3 have the polymerizable monomer of phosphate or thiophosphoric acid base the time, obtain showing the solidification compound of excellent cementability for wetting body, particularly dentine.
[changing 1]
[in the formula, R
1Be hydrogen or methyl, R
2Be that carbonatoms is (l+n) valency group of 2～40, l is 1～5 integer, and m is 0 or 1, and n is 1～4 integer ,-X-is-O-or-NH-,-Y-is-O-or-S-, Z
1, Z
2And Z
3Be Sauerstoffatom or sulphur atom independently of one another.]
[changing 2]
[in the formula, R
1Be hydrogen or methyl, x is 4～20 integer, and m is 0 or 1 ,-X-is-O-or-NH-,-Y-is-O-or-S-, Z
1, Z
2And Z
3Be Sauerstoffatom or sulphur atom independently of one another.]
[changing 3]
[in the formula, R
1Be hydrogen or methyl, R
3Be that carbonatoms is (y+n) valency group of 3～10, y is 2～5 integer, and m is 0 or 1, and n is 1～4 integer ,-X-is-O-or-NH-,-Y-is-O-or-S-, Z
1, Z
2, Z
3Be Sauerstoffatom or sulphur atom independently of one another.]
In the scope that can constitute liquid free radical polymerization monomer (a), the free radical polymerization monomer of as above enumerating uses with the form of the combination more than a kind or 2 kinds or 2 kinds.Be noted that; in this specification sheets; term " (methyl) vinylformic acid " is the general name of " vinylformic acid " and " methacrylic acid "; term " (methyl) acrylate " is the general name of " acrylate " and " methacrylic ester ", and term " (methyl) acryl " is the general name of " acryl " and " methacryloyl ".
Organo-peroxide (b) is the oxidizer composition of reductionoxidation polymerization initiator.As organo-peroxide (b), can enumerate diacyl peroxide class, peroxyesters, dialkyl peroxide class, peroxy ketal class, ketone peroxide class, hydroperoxide.As the object lesson of diacyl peroxide class, can enumerate toluyl between benzoyl peroxide, peroxidation 2,4 dichloro benzene formyl, peroxidation.Object lesson as peroxyesters, can enumerate t-butyl per(oxy)benzoate, dual-tert-butyl peroxide isophthalic acid ester, 2,5-dimethyl-2, two (benzoyl peroxide) hexanes of 5-, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide sec.-propyl carboxylicesters.As the object lesson of dialkyl peroxide class, can enumerate dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide.As the object lesson of peroxy ketal class, can enumerate 1, two (tert-butyl peroxides) 3,3 of 1-, 5-trimethyl-cyclohexane, 1, two (tert-butyl peroxide) hexanaphthenes, 1 of 1-, two (the peroxidation uncle hexyl) hexanaphthenes of 1-.As the object lesson of ketone peroxide class, can enumerate methylethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate superoxide.As the object lesson of hydroperoxide type, can enumerate tert-butyl hydroperoxide, cumene hydroperoxide, peroxidation to diisopropyl benzene.
Powdery, water-soluble reductibility compound (c) is the reductive agent composition of reductionoxidation polymerization initiator.As mentioned above, maximum characteristics of the present invention are that powdery, water-soluble reductibility compound (c) is not to be dissolved in the water system solidification compound, but are scattered in the non-water system solidification compound." non-water system " alleged among the present invention is meant not specially hydrous water, negates the meaning that contains the micro-moisture of sneaking into inevitably and should not be construed as.In addition, alleged " water-soluble " is meant under the room temperature (25 ℃) that the solubleness in water is 0.5mg/100mL or more than the 0.5mg/100mL among the present invention.As powdery, water-soluble reductibility compound (c), preferred described solubleness is 1mg/100mL or the above powdery, water-soluble reductibility compound of 1mg/100mL.As powdery, water-soluble reductibility compound (c), can enumerate each powder of sulphite, hydrosulphite, pyrosulfite, thiosulphate, polythionate (チ オ ン Suan salt), hyposulfite.In these examples, from low, the water-soluble height of the solvability liquid free radical polymerization monomer (a), consider as the aspects such as ability height of reductive agent, each powder of preferred sulphite, hydrosulphite, wherein, the powder of sulphite such as S-WAT, potassium sulfite, calcium sulfite, ammonium sulphite, sodium bisulfite, Potassium hydrogen sulfite most preferably.Be noted that, the dispersion state of above-mentioned powdery, water-soluble reductibility compound (c) in composition in the present composition can followingly be confirmed: make the present composition after solidifying under the environment that does not have water, make the cured article fracture, this surface of fracture is measured with small fluorescent x-ray analyzer of energy dispersion type.
Median size to powdery, water-soluble reductibility compound (c) is unqualified, if but excessive then free settling, so be preferably 500 μ m or below the 500 μ m, 100 μ m or below the 100 μ m more preferably.On the other hand, if median size is too small, then the specific surface area of powder is excessive, can be in liquid free radical polymerization monomer (a) the dispersive amount reduce, so be preferably 0.01 μ m or more than the 0.01 μ m.That is, the median size of powdery, water-soluble reductive agent compound (c) is preferably in the scope of 0.01～500 μ m, more preferably in the scope of 0.01～100 μ m.
For the shape of powdery, water-soluble reductibility compound (c), can enumerate different shapes such as sphere, needle-like, tabular, broken shape, do not limit especially.Powdery, water-soluble reductibility compound (c) can pass through known method making in the past such as comminuting method, freeze-drying.
With respect to liquid free radical polymerization monomer (a) 100 weight parts, the preferred use level of organo-peroxide (b) and powdery, water-soluble reductibility compound (c) is respectively 0.05～10 weight part (0.1～5 weight part more preferably) and 0.01～15 weight part (0.05～10 weight part more preferably).
The polymerizable monomer that use contains acidic-group is during as liquid free radical polymerization monomer (a) a part of, with respect to liquid free radical polymerization monomer (a) 100 weight parts except the polymerizable monomer that contains acidic-group, preferred polymerizable monomer 1～200 weight part (5～150 weight parts more preferably) that contains acidic-group that cooperates.
In order to adjust the set time of the present composition, as the reductive agent composition of reductionoxidation polymerization initiator, also can be with known aromatic amine, aromatic nitrile base, aromatic series-sulfinate etc. and powdery, water-soluble reductibility compound (c) and usefulness.But, cooperate too much these arbitrarily the reductive agent composition greatly shorten usable time sometimes, therefore must be noted.
As aromatic amine or aromatic nitrile base, can enumerate methylphenylamine, N-methyl para-totuidine, N-methyl meta-aminotoluene, N-methyl Ortho Toluidine, N-ethanol para-totuidine, N-ethanol meta-aminotoluene, N-ethanol Ortho Toluidine, to the methylamino ethyl benzoate, between the methylamino ethyl benzoate, adjacent methylamino ethyl benzoate, to the methylamino methyl-phenoxide, between the methylamino methyl-phenoxide, adjacent methylamino methyl-phenoxide, 1-methylamino naphthalene, 2-methylamino naphthalene, N, accelerine, N, the N-dimethyl-p-toluidine, N, N-dimethyl meta-aminotoluene, N, N-dimethyl Ortho Toluidine, N, the N-DEPT, N, N-di-alcohol meta-aminotoluene, N, N-di-alcohol Ortho Toluidine, the ESCAROL 507 ethyl ester, between the dimethylaminobenzoic acid ethyl ester, adjacent dimethylaminobenzoic acid ethyl ester, to the dimethylamino methyl-phenoxide, between the dimethylamino methyl-phenoxide, adjacent dimethylamino methyl-phenoxide, 1-dimethylamino naphthalene, 2-dimethylamino naphthalene.With respect to liquid free radical polymerization monomer (a) 100 weight parts, the preferred use level of aromatic amine or aromatic nitrile base is 0.01～10 weight part (0.03～5 weight part more preferably).
As the aromatic series-sulfinate, can enumerate benzene sulfinic acid, to toluenesulfinic acid, adjacent toluenesulfinic acid, ethylbenzene-sulfinic acid, decyl benzene sulfinic acid, dodecyl benzene sulfinic acid, 2,4,6-Three methyl Benzene-sulfinic acid, 2,4, lithium salts, sodium salt, sylvite, rubidium salt, cesium salt, magnesium salts, calcium salt, strontium salt, molysite, mantoquita, zinc salt, ammonium salt, tetramethyl ammonium, the tetraethyl-ammonium salt of 6-triisopropyl benzene sulfinic acid, chlorobenzene-sulfinic acid, naphthalene sulfinic acid etc.With respect to liquid free radical polymerization monomer (a) 100 weight parts, the preferred use level of aromatic series-sulfinate is 0.01～10 weight part (0.03～5 weight part more preferably).
In order to improve the physical strength after the curing, can in the present composition, cooperate the glass weighting material.The glass weighting material that is cooperated can use any one of non-stripping property glass weighting material or stripping property glass weighting material, also can and use both in addition.As non-stripping property glass weighting material, can enumerate mineral-type weighting material, organic class weighting material and their complex body weighting material.As the mineral-type weighting material, can enumerate silicon-dioxide; With silicon-dioxide is base material, contains the mineral of kaolin, clay, mica (mother Cloud), mica (マ イ カ) etc.; With silicon-dioxide is base material, contains Al
2O
3, B
2O
3, TiO
2, ZrO
2, BaO, La
2O
3, SrO
2, CaO, P
2O
5Deng ceramic-like; And category of glass such as lanthanum glass, barium glass, strontium glass.In addition, as the mineral-type weighting material, also can cooperate crystal quartz, hydroxyapatite, aluminum oxide, titanium oxide, ytterbium oxide, fluoridize ytterbium, zirconium white, barium sulfate etc.As organic class weighting material, can enumerate organic resins such as polymethylmethacrylate, polymeric amide, polystyrene, polyvinyl chloride, neoprene, paracril, styrene butadiene rubbers.As the complex body weighting material, can enumerate the weighting material that in above-mentioned organic resin, disperses non-stripping property glass weighting material and obtain; Be coated with the surface of non-stripping property weighting material and the weighting material that obtains with above-mentioned organic resin.As stripping property glass weighting material, (for example can enumerate valent stripping property positively charged ion that can have more than 2 or 2 with containing of the polymerizable monomer reaction that contains acidic-group, strontium, calcium, zinc, aluminium, iron, zirconium etc.) aluminum fluoride glass (for example, calcium aluminum fluoride glass, strontium aluminum fluoride glass, barium aluminum fluoride glass, strontium calcium aluminum fluoride glass).These weighting materials can carry out using after the surface treatment with known surface treatment agents such as silane coupling agents as required in advance.As surface treatment agent, can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, vinyl trichloro silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, γ-Huan Yangbingyangbingjisanjiayangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan, γ-An Jibingjisanyiyangjiguiwan.
Applicable object is an organism sclerous tissues, particularly during tooth, can cooperate the known water soluble fluoridized compound that emit fluorion with the amount that does not reduce the cementability degree in the present composition.As water soluble fluoridized compound, for example can enumerate lithium fluoride, Sodium Fluoride, Potassium monofluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, magnesium fluoride, Calcium Fluoride (Fluorspan), strontium fluoride, barium fluoride, zinc fluoride, aluminum fluoride, manganous fluoride, cupric fluoride, plumbous fluoride, silver fluoride, antimonic fluoride, cobaltous fluoride, fluoridize bismuth, Tin tetrafluoride., fluorinated diamine silver (Off Star ジ ア Application ミ ン Silver), sodium monoflurophosphate, potassium fluotitanate, fluostannate, silicofluoride.Water soluble fluoridized compound can use a kind separately, perhaps also can be also with multiple.During hydrous water dissolubility fluorinated compound, preferably the method for record is made particulate in open clear 2-258602 communique etc. by the spy, perhaps opens the method put down in writing in the flat 10-36116 communique by the spy and cooperates with the polysiloxane back that is covered.
In the present composition, can cooperate known stablizer, Photoepolymerizationinitiater initiater, dyestuff, pigment.
As the packaging means of the present composition, consider to be preferably the subpackage mode from the storage stability aspect.As the subpackage mode, be preferably the 1st dose of containing liquid free radical polymerization monomer (a) and organo-peroxide (b) and the 2nd dose 2 subpackages that contain liquid free radical polymerization monomer (a) and powdery, water-soluble reductibility compound (c).In the present composition, cooperate when containing the polymerizable monomer of acidic-group, be preferably 2 subpackages of the 1st dose and the 2nd dose, described the 1st dose contains liquid free radical polymerization monomer (a) and organo-peroxide (b), and wherein said liquid free radical polymerization monomer (a) contains the polymerizable monomer of acidic-group; Described the 2nd dose contains liquid free radical polymerization monomer (a) and powdery, water-soluble reductibility compound (c), and wherein said liquid free radical polymerization monomer (a) does not contain the polymerizable monomer of acidic-group.Cooperate when containing the polymerizable monomer of acidic-group, it is matched with in the 1st dose is because if it is matched with in the 2nd dose, then there is the trend of freeradical yield reduction in powdery, water-soluble reductibility compound (c) such as an alkali metal salt and contain the polymerizable monomer reaction of acidic-group and decompose in the storage.
The present composition is packetized into the 1st dose that contains liquid free radical polymerization monomer (a) and organo-peroxide (b); And contain liquid free radical polymerization monomer (a) and powdery, water-soluble reductibility compound (c) the 2nd dose when using, the 1st dose is with respect to liquid free radical polymerization monomer (a) 100 weight parts, cooperate organo-peroxide (b) 0.1～50 weight part to prepare, on the other hand, the 2nd dose is with respect to liquid free radical polymerization monomer (a) 100 weight parts, cooperate powdery, water-soluble reductibility compound (c) 0.1～50 weight part to prepare, the 1st dose and the 2nd dose mix use with 1: 10～10: 1 scope of weight ratio.
When packaging means is the subpackage mode of the 1st dose and the 2nd dose, before will using, be mixed and made into 1 dose with the 1st dose and the 2nd dose after, be applied to wetting body.Contact by the moisture of mixture with the wetting body surface, promote the curing reaction speed of bonding interface portion, by finishing this curing reaction, the present composition is mutually bonding with wetting body.If with the situation that is applied to tooth is that example describes, then as described below.That is, fill when repairing tooth nest hole, behind ordinary method cleaning tooth nest hole, the present composition of making 1 dose is filled in the tooth nest hole.To be preced with, during patchery thing cementation such as mosaic, after the bonding plane cleaning with the bonding plane in abutment or tooth nest hole and patchery thing, at least 1 face the present composition of making 1 dose being coated the bonding plane of the bonding plane of tooth nest hole or abutment or patchery thing carries out cementation.Be noted that, the present composition is coated before the dental surface, can be implemented following known pre-treatment to dental surface: the modification that utilize etch processes that acidic aqueous solution carries out, utilizes priming paint to carry out handles, utilize etching-modification synchronous processing that priming paint with etch capabilities carries out etc.
Embodiment
The present invention will be described in more detail by embodiment.The present invention is not subjected to the qualification of following embodiment.Hereinafter employed abbreviation is as described below.
Bis-GMA:2, two [4-(3-methacryloxy-2-hydroxyl propoxy-) phenyl] propane of 2-
TEGDMA: triethylene glycol dimethacrylate
NPG: neopentylglycol dimethacrylate
HEMA:2-hydroxyethyl methacrylic ester
MDP:10-methacryloxy decyl dihydrogen phosphoric acid ester
BPO: benzoyl peroxide
DEPT:N, the N-DEPT
TPBSS:2,4,6-triisopropyl benzene sulfinic acid sodium
(embodiment 1)
Preparation following A 1-1 agent and A1-2 agent, with A1-1 agent and A1-2 agent combination, the weight ratio for preparing both is the non-water system solidification compound of 1: 1 subpackage type (present composition).S-WAT in the composition that mixing A1-1 agent and A1-2 agent form is a dispersion state.The non-water system solidification compound of this subpackage type is carried out test (P1) and the stretching bonding strength test (Q1) of following set time, try to achieve set time and stretching bonding strength.The result is as shown in table 1.The median size that is noted that powdery, water-soluble reductibility compound (being the S-WAT powder under the situation of embodiment 1) is that dispersion medium is measured (following embodiment also adopts same measuring method) with ethanol with laser diffraction formula size-grade distribution device SALD-2100 (island Jin She system).
The A1-1 agent:
Bis-GMA 40 weight parts
HEMA 20 weight parts
TEGDMA 20 weight parts
MDP 20 weight parts
BPO 1 weight part
The A1-2 agent:
Bis-GMA 40 weight parts
HEMA 40 weight parts
TEGDMA 20 weight parts
S-WAT powder (median size is 6.1 μ m) 3 weight parts
[test of set time (P1)]
At diameter is that 1cm, the degree of depth are to add A1-1 agent and A1-2 agent 0.1g respectively in the hemispherical resin container of 5mm, makes 1 dose with the scraper thorough mixing.In this liquor, insert the thermopair (society of the rugged making in ridge institute system) that links to each other with recording gauge (Yokogawa Motor society system) after the mixing immediately, follow the temperature variation of polymerization curing reaction with the recording gauge record, try to achieve set time (after the mixing) until the time that forms exothermic peak.
[test of stretching bonding strength (Q1)]
Under flowing water, grind the labial surface of ox lower jaw front tooth, form enamel or 2 kinds of tabular surfaces of dentine with the carborundum paper (paper society system is ground by Japan) of #80.Use the carborundum paper (paper society system is ground by Japan) of #1000 under flowing water, further to grind to tabular surface, make even surface.Paste on even surface that to have diameter be the adhesive tape that the thickness of the circular hole of 4mm is about 150 μ m, limit bond area.In above-mentioned circular hole, use the mixture of coating A1-1 agent of fine, soft fur pen and A1-2 agent then.Make coating thickness be about 100 μ m.Commercially available photo-polymerization type tooth section compound resin (the Network ラ レ メ デ ィ カ Le corporate system of mounting on this coated face, trade(brand)name " Network リ ア Off イ Le AP-X "), with tooth section radiation of visible light device (J.Morita USA system, trade(brand)name " JET ラ イ ト 3000 ") carries out 40 seconds rayed, make its curing.On resulting cured article, use commercially available tooth section to obtain test film with an end of the cylindrical rod of the SUS304 system of the bonding 7mm φ * 25mm of resin cement (Network ラ レ メ デ イ カ Le corporate system, trade(brand)name " パ Na PVC ア Off Le オ ロ セ メ Application ト ").After bonding 1 hour test film be impregnated in 37 ℃ the water, from water, take out after 24 hours, use universal testing machine (society of Shimadzu Seisakusho Ltd. system) to measure the stretching bonding strength.When stretching determining bonding strength, pinblock speed (Network ロ ス ヘ Star De ス ピ one De) is set at 2mm/ minute.With the mean value of the measured value of 8 test films stretching bonding strength as test film.
(embodiment 2)
Change S-WAT powder 3 weight parts in the A1-2 agent of embodiment 1 into potassium sulfite powder 2 weight parts, the A2-2 agent for preparing following composition, make up the A1-1 agent of this A2-2 agent and embodiment 1, the weight ratio for preparing both is the non-water system solidification compound of 1: 1 subpackage type (present composition).Potassium sulfite in the composition that mixing A2-2 agent and A1-1 agent form is a dispersion state.The non-water system solidification compound of this subpackage type is carried out the test (P1) of above-mentioned set time and the test (Q1) of stretching bonding strength, try to achieve set time and stretching bonding strength.The result is as shown in table 1.
The A2-2 agent:
Bis-GMA 40 weight parts
HEMA 40 weight parts
TEGDMA 20 weight parts
Potassium sulfite powder (median size is 9.9 μ m) 2 weight parts
(comparative example 1)
In the A1-2 of embodiment 1 agent, add entry 10 weight parts, preparation following A 3-2 agent, the A1-1 agent of making up this A3-2 agent and embodiment 1, the weight ratio for preparing both is 1: 1 a subpackage type water system solidification compound.S-WAT in the composition that mixing A3-2 agent and A1-1 agent form is a dissolved state.This subpackage type water system solidification compound is carried out the test (P1) of above-mentioned set time and the test (Q1) of stretching bonding strength, try to achieve set time and stretching bonding strength.The result is as shown in table 1.
The A3-2 agent:
Bis-GMA 40 weight parts
HEMA 40 weight parts
TEGDMA 20 weight parts
Water 10 weight parts
S-WAT powder (median size is 6.1 μ m) 3 weight parts
(comparative example 2)
Change the use level of the S-WAT powder in the A3-2 agent of comparative example 1 into 0.1 weight part by 3 weight parts, preparation following A 4-2 agent, the A1-1 agent of making up this A4-2 agent and embodiment 1, the weight ratio for preparing both is 1: 1 a subpackage type water system solidification compound.S-WAT in the composition that mixing A4-2 agent and A1-1 agent form is a dissolved state.This subpackage type water system solidification compound is carried out the test (P1) of above-mentioned set time and the test (Q1) of stretching bonding strength, try to achieve set time and stretching bonding strength.The result is as shown in table 1.
The A4-2 agent:
Bis-GMA 40 weight parts
HEMA 40 weight parts
TEGDMA 20 weight parts
Water 10 weight parts
S-WAT powder (median size is 6.1 μ m) 0.1 weight part
[table 1]
As shown in table 1, for the present composition of embodiment 1 and 2 preparations, the set time of composition in its entirety is so not short.Though this supposition is because these compositions contain a large amount of water-soluble reductibility compounds, does not contain water, so the freeradical yield of composition inside is not so much.In addition, the present composition for embodiment 1 and 2 preparations carries out fast at the bonding interface polymerization curing reaction, shows high bonding strength.This supposition is to suppress (Heng Lying because these compositions can produce in the bonding interface portion that has water) because the caused polymerization of oxygen hinders a large amount of free radical of degree.On the other hand, the water system solidification compound of comparative example 1 preparation solidifies when mixing, in addition, the water system solidification compound of comparative example 2 preparations is low to Dentinal bonding strength, the set time of the water system solidification compound of comparative example 1 preparation is extremely short, this may be because S-WAT is a dissolved state, the cause of carrying out fast after mixing with the redox reaction of BPO (benzoyl peroxide).The water system solidification compound of comparative example 2 preparations is low to Dentinal bonding strength, this may be because, for the usable time that makes solidification compound for can the practical time, reduced the use level of S-WAT powder, the result does not have to produce the free radical that can suppress to hinder owing to the caused polymerization of the oxygen of bonding interface portion the abundant amount of degree.
(embodiment 3)
Prepare following B1-1 agent and B1-2 agent, make up these 2 doses, the weight ratio for preparing both is the non-water system solidification compound of 1: 1 subpackage type (present composition).S-WAT in the composition that mixing B1-1 agent and B1-2 agent form is a dispersion state.The non-water system solidification compound of this subpackage type is carried out the test (P1) of above-mentioned set time, try to achieve set time, in addition, carry out the test (Q2) of following stretching bonding strength, try to achieve the stretching bonding strength.The result is as shown in table 2.
The B1-1 agent:
Bis-GMA 40 weight parts
HEMA 30 weight parts
NPG 30 weight parts
BPO 1 weight part
The B1-2 agent:
Bis-GMA 40 weight parts
HEMA 30 weight parts
NPG 30 weight parts
S-WAT powder (median size is 6.1 μ m) 1 weight part
[test of stretching bonding strength (Q2)]
Under flowing water, grind the labial surface of ox lower jaw front tooth, form enamel or 2 kinds of tabular surfaces of dentine with the carborundum paper (paper society system is ground by Japan) of #80.Use the carborundum paper (paper society system is ground by Japan) of #1000 under flowing water, tabular surface further to be ground, make even surface.Paste on even surface that to have diameter be the adhesive tape that the thickness of the circular hole of 4mm is about 150 μ m, limit bond area.Then in above-mentioned circular hole, use the writing brush coating to contain the paint base composition of the MDP of the HEMA of water, 25 weight parts of 65 weight parts and 10 weight parts, directly place after 30 seconds, the flowability that is dried to paint base composition with air syringe (エ ア one シ リ Application ジ) disappears.Then, on the coated face of paint base composition, use the mixture of coating B1-1 agent of fine, soft fur pen and B1-2 agent.Make coating thickness be about 100 μ m.The commercially available photo-polymerization type tooth section compound resin (above-mentioned " Network リ ア Off イ Le AP-X ") of mounting carries out 40 seconds rayed with tooth section with visible rays irradiator (above-mentioned " JET ラ イ ト 3000 ") on this coated face, makes its curing.On resulting cured article, use commercially available tooth section to obtain test film with an end of the cylindrical rod of the SUS304 system of the bonding 7mm φ * 25mm of resin cement (above-mentioned " パ Na PVC ア Off Le オ ロ セ メ Application ト ").After bonding 1 hour test film be impregnated in 37 ℃ the water, from water, take out after 24 hours, use universal testing machine (Shimadzu Seisakusho Ltd.'s system) to measure the stretching bonding strength.During the mensuration of the bonding strength that stretches, it is 2mm/ minute with the pinblock speed setting.With the mean value of the measured value of 8 test films stretching bonding strength as test film.
(embodiment 4)
Prepare following B2-2 agent, with the B1-1 agent combination of itself and embodiment 3, the weight ratio for preparing both is the non-water system solidification compound of 1: 1 subpackage type (present composition).In the B2-2 agent, the sodium bisulfite that mixes in the composition that B1-1 agent and B2-2 agent form is dispersion state.The non-water system solidification compound of this subpackage type is carried out the test (P1) of above-mentioned set time and the test (Q2) of stretching bonding strength, try to achieve set time and stretching bonding strength.The result is as shown in table 2.
The B2-2 agent:
Bis-GMA 40 weight parts
HEMA 40 weight parts
NPG 20 weight parts
Sodium bisulfite powder (median size is 8.1 μ m) 2 weight parts
(comparative example 3)
Prepare following B3-2 agent, with the B1-1 agent combination of itself and embodiment 3, the weight ratio for preparing both is the non-water system solidification compound of 1: 1 subpackage type.The non-water system solidification compound of this subpackage type is carried out the test (P1) of above-mentioned set time and the test (Q2) of stretching bonding strength, try to achieve set time and stretching bonding strength.The result is as shown in table 2.
The B3-2 agent:
Bis-GMA 40 weight parts
HEMA 40 weight parts
NPG 20 weight parts
DEPT 1 weight part
(comparative example 4)
Prepare following B4-2 agent, with the B1-1 agent combination of itself and embodiment 3, the weight ratio for preparing both is 1: 1 a subpackage type water system solidification compound.S-WAT in the composition that mixing B4-2 agent and B1-1 agent form is a dissolved state.This subpackage type water system solidification compound is carried out the test (P1) of above-mentioned set time and the test (Q2) of stretching bonding strength, try to achieve set time and stretching bonding strength.The result is as shown in table 2.
The B4-2 agent:
Bis-GMA 40 weight parts
HEMA 40 weight parts
NPG 20 weight parts
Water 10 weight parts
S-WAT powder (median size is 6.1 μ m) 0.1 weight part
[table 2]
As shown in table 2, be can the practical time set time of the present compositions of embodiment 3 and 4 preparations, and enamel and dentine are all shown excellent bonding strength.On the other hand, the water system solidification compound of the non-water system solidification compound of comparative example 3 preparations and comparative example 4 preparations is all low to Dentinal bonding strength.The non-water system solidification compound of comparative example 3 preparations thinks that to Dentinal bonding strength is low reason is as follows: owing to use the reductive agent of water-insoluble DEPT as the reductionoxidation polymerization initiator, because the caused polymerization of oxygen hinders, the water system solidification compound of bonding interface portion does not have abundant polymerizing curable.The water system solidification compound of comparative example 4 preparations is presumed as follows the low reason of Dentinal bonding strength: in order to make usable time for can greatly having reduced the use level of S-WAT the practical time, because the caused polymerization of oxygen hinders, the water system solidification compound of bonding interface portion does not have abundant polymerizing curable.
(embodiment 5～7 and comparative example 5)
The non-water system solidification compound of forming shown in the preparation table 3 of 4 kinds of subpackage types (2 doses weight ratio all is 1: 1).Water-soluble reductibility compound [S-WAT (median size is 6.1 μ m) or calcium sulfite (median size is 12.3 μ m)] in the 1st dose of the non-water system solidification compound of subpackage type of mix embodiment 5～7 and the 2nd dose of composition that forms is a dispersion state.The non-water system solidification compound of these subpackage types is carried out the test (P1) of above-mentioned set time and the test (Q2) of stretching bonding strength, try to achieve set time and stretching bonding strength.The result is as shown in table 4.
[table 3]
[table 4]
As shown in table 4, be can the practical time set time of the present composition of embodiment 5～7 preparation, and enamel and dentine are all shown excellent bonding strength.On the other hand, the non-water system solidification compound of comparative example 5 preparations is low to Dentinal bonding strength.The non-water system solidification compound of comparative example 5 preparation is presumed as follows the low reason of Dentinal bonding strength: owing to use the reductibility compound (DEPT and TPBSS) that is dissolved in the composition reductive agent as the reductionoxidation polymerization initiator, the frequency that organo-peroxide and reductibility compound meet with molecularity in composition is higher, help the reductibility compound of polymerization curing reaction to reduce in bonding interface portion, the non-water system solidification compound of bonding interface portion does not have abundant polymerizing curable.
(embodiment 8)
Prepare following D1-1 agent and D1-2 agent, make up these 2 doses, the weight ratio for preparing both is the non-water system solidification compound of 1: 1 subpackage type (present composition).S-WAT in the composition that mixing D1-1 agent and D1-2 agent form is a dispersion state.The non-water system solidification compound of this subpackage type is carried out the test (P2) of following set time and try to achieve set time, carry out the test (Q3) of following shear bond strength in addition and try to achieve shear bond strength.The result is as shown in table 5.
The D1-1 agent
Bis-GMA 40 weight parts
HEMA 20 weight parts
TEGDMA 20 weight parts
MDP 20 weight parts
BPO 1 weight part
Silanization silica powder 300 weight parts
The D1-2 agent
Bis-GMA 40 weight parts
HEMA 40 weight parts
TEGDMA 20 weight parts
S-WAT powder (median size is 6.1 μ m) 2 weight parts
DEPT 1 weight part
TPBSS 1 weight part
Silanization silica powder 300 weight parts
(comparative example 6)
Remove the S-WAT powder from the D1-2 agent of embodiment 8, prepare following D2-2 agent, with the D1-1 agent combination of itself and embodiment 8, the weight ratio for preparing both is the non-water system solidification compound of 1: 1 subpackage type.The test (P2) that this subpackage type water system solidification compound carries out following set time is tried to achieve set time, carry out the test (Q3) of following shear bond strength in addition and try to achieve shear bond strength.The result is as shown in table 5.
The D2-2 agent
Bis-GMA 40 weight parts
HEMA 40 weight parts
TEGDMA 20 weight parts
DEPT 1 weight part
TPBSS 1 weight part
Silanization silica powder 300 weight parts
[test of set time (P2)]
Take by weighing D1-1 agent and D1-2 agent or D2-2 agent 0.2g respectively, fully be made of mixing paste with scraper.It is that 1cm, the degree of depth are in the hemispherical resin container of 5mm that this paste is added diameter immediately, insert the thermopair (society of the rugged making in ridge institute system) that links to each other with recording gauge (Yokogawa Motor society system), follow the temperature variation of polymerization curing reaction with the recording gauge record, try to achieve set time (after mixing) until the time that forms exothermic peak.
[test of shear bond strength (Q3)]
Under flowing water, grind the labial surface of ox lower jaw front tooth, form enamel or 2 kinds of tabular surfaces of dentine with the carborundum paper (paper society system is ground by Japan) of #80.In with the stainless steel rounding tube of bottom back cover, drop into tooth section compound resin, ox lower jaw front tooth is imbedded this tooth section with in the compound resin, and tabular surface is not buried.Tooth section removes bottom after solidifying with compound resin, uses the carborundum paper (paper society system is ground by Japan) of #1000 further to grind under flowing water to the tabular surface that exposes, and makes even surface.Paste on even surface that to have diameter be the adhesive tape that the thickness of the circular hole of 4mm is about 150 μ m, limit bond area.At the round shape tetrafluoroethylene molding jig of the position of above-mentioned circular hole (bonding plane) mounting internal diameter 4mm * height 2mm, in cylinder, fill the paste that mixes D1-1 agent and D1-2 agent or D2-2 agent and obtain then.Fill after 1 hour, remove round shape tetrafluoroethylene molding jig, make test film.This test film be impregnated in 37 ℃ the water, from water, take out after 24 hours, use universal testing machine (イ Application ス ト ロ Application corporate system) to measure shear bond strength.When carrying out the mensuration of shear bond strength, it is 2mm/ minute with the pinblock speed setting.With the mean value of the measured value of 8 test films as shear bond strength.
[table 5]
As shown in table 5, be can the practical time set time of the present composition of embodiment 8 preparation, and enamel and dentine are all shown excellent bonding strength.On the other hand, the non-water system solidification compound of comparative example 6 preparations is low to Dentinal bonding strength.The non-water system solidification compound of comparative example 6 preparation is presumed as follows the low reason of Dentinal bonding strength: owing to use the reductibility compound (DEPT and TPBSS) that is dissolved in the composition reductive agent as the reductionoxidation polymerization initiator, the frequency height that organo-peroxide and reductibility compound meet with molecularity in composition, help the reductibility compound of polymerization curing reaction to reduce in bonding interface portion, the non-water system solidification compound of bonding interface portion does not have abundant polymerizing curable.For owing to the oxygen that is present in the dentine is vulnerable to the dentine that polymerization hinders, observe significant bonding force and reduce.
(embodiment 9)
Prepare following E1-1 agent and E1-2 agent, make up these 2 doses, the weight ratio for preparing both is the non-water system solidification compound of 1: 1 subpackage type (present composition).S-WAT in the composition that mixing E1-1 agent and E1-2 agent form is a dispersion state.The non-water system solidification compound of this subpackage type is carried out the test (P2) of above-mentioned set time and try to achieve set time, carry out the test (Q4) of following shear bond strength in addition and try to achieve shear bond strength.The result is as shown in table 6.
The E1-1 agent
Bis-GMA 40 weight parts
HEMA 20 weight parts
TEGDMA 20 weight parts
MDP 20 weight parts
BPO 1 weight part
Silanization silica powder 300 weight parts
The E1-2 agent
Bis-GMA 40 weight parts
HEMA 40 weight parts
TEGDMA 20 weight parts
S-WAT powder (median size is 6.1 μ m) 4 weight parts
DEPT 1 weight part
TPBSS 1 weight part
Aluminum fluoride glass GM35429 (シ ョ ッ ト corporate system) 300 weight parts
(comparative example 7)
Remove the S-WAT powder from the E1-2 agent of embodiment 9, prepare following E2-2 agent, with the E1-1 agent combination of itself and embodiment 9, the weight ratio for preparing both is the non-water system solidification compound of 1: 1 subpackage type.The test (P2) that this subpackage type water system solidification compound carries out above-mentioned set time is tried to achieve set time, carry out the test (Q4) of following shear bond strength in addition and try to achieve shear bond strength.The result is as shown in table 6.
The E2-2 agent
Bis-GMA 40 weight parts
HEMA 40 weight parts
TEGDMA 20 weight parts
DEPT 1 weight part
TPBSS 1 weight part
Aluminum fluoride glass GM35429 (シ ョ Star ト corporate system) 300 weight parts
[test of shear bond strength (Q4)]
Under flowing water, grind the labial surface of ox lower jaw front tooth, form enamel or 2 kinds of tabular surfaces of dentine with the carborundum paper (paper society system is ground by Japan) of #80.In with the stainless steel rounding tube of bottom back cover, drop into tooth section compound resin, ox lower jaw front tooth is imbedded this tooth section with in the compound resin, and tabular surface is not buried.Tooth section removes bottom and stainless steel rounding tube after solidifying with compound resin, uses the carborundum paper (paper society system is ground by Japan) of #1000 further to grind under flowing water to the tabular surface that exposes, and makes even surface.Paste on even surface that to have diameter be the adhesive tape that the thickness of the circular hole of 4mm is about 150 μ m, limit bond area.In above-mentioned circular hole, contain the paint base composition of the MDP of the HEMA of water, 25 weight parts of 65 weight parts and 10 weight parts then, places after 30 seconds, be dried to the flowability disappearance of paint base composition with air syringe with writing brush coating.Then, at the round shape tetrafluoroethylene molding jig of the position of above-mentioned circular hole (bonding plane) mounting internal diameter 4mm * height 2mm, in cylinder, fill the paste that mixes E1-1 agent and E1-2 agent or E2-2 agent and obtain.Fill after 1 hour, remove round shape tetrafluoroethylene molding jig, make test film.This test film be impregnated in 37 ℃ the water, from water, take out after 24 hours, use universal testing machine (イ Application ス ト ロ Application corporate system) to measure shear bond strength.When carrying out the mensuration of shear bond strength, it is 2mm/ minute with the pinblock speed setting.With the mean value of the measured value of 8 test films as shear bond strength.
[table 6]
As shown in table 6, be can the practical time set time of the present composition of embodiment 9 preparation, and enamel and dentine are all shown the excellent shear bonding strength.On the other hand, the non-water system solidification compound of comparative example 7 preparations is low to Dentinal shear bond strength.The non-water system solidification compound of comparative example 7 preparation is presumed as follows the low reason of Dentinal shear bond strength: owing to use the reductibility compound (DEPT and TPBSS) that is dissolved in the composition reductive agent as the reductionoxidation polymerization initiator, the frequency height that organo-peroxide and reductibility compound meet with molecularity in composition, help the reductibility compound of polymerization curing reaction to reduce in bonding interface portion, the non-water system solidification compound of bonding interface portion does not have abundant polymerizing curable.For owing to the oxygen that is present in the dentine is vulnerable to the dentine that polymerization hinders, observe significant bonding force and reduce.
Claims (5)
1. the organism sclerous tissues caking agent that contains redox curing-type nonaqueous curable composition, wherein said redox curing-type nonaqueous curable composition contains liquid free radical polymerization monomer (a), organo-peroxide (b) and powdery, water-soluble reductibility compound (c), described liquid free radical polymerization monomer (a) is for being selected from α-Qing Jibingxisuanzhi, (methyl) acrylate, the alpha-halogen acrylate, crotonate, laurate, sorbic ester, maleic acid ester, itaconic ester, (methyl) acrylamide, vinyl ester, vinyl ether and cinnamic at least a, described powdery, water-soluble reductibility compound (c) is for being selected from the sulphite powder, the hydrosulphite powder, the pyrosulfite powder, the thiosulphate powder, polythionate powder and hyposulfite powder at least a, in this redox curing-type nonaqueous curable composition, with respect to the liquid free radical polymerization monomer (a) of 100 weight parts, contain 0.05～10 weight part organo-peroxide (b) and 0.01～15 weight part powdery, water-soluble reductibility compound (c), and the water-soluble reductibility compound of dispersed powders shape (c) forms in liquid free radical polymerization monomer (a).
2. the described organism sclerous tissues caking agent that contains redox curing-type nonaqueous curable composition of claim 1, wherein, described powdery, water-soluble reductibility compound (c) is the sulphite powder.
3. the described organism sclerous tissues caking agent that contains redox curing-type nonaqueous curable composition of claim 1, wherein, described redox curing-type nonaqueous curable composition is packetized into the 1st dose that contains liquid free radical polymerization monomer (a) and organo-peroxide (b); With contain liquid free radical polymerization monomer (a) and powdery, water-soluble reductibility compound (c) the 2nd dose.
4. the described organism sclerous tissues caking agent that contains redox curing-type nonaqueous curable composition of claim 3, wherein, powdery, water-soluble reductibility compound (c) is the sulphite powder.
5. the described organism sclerous tissues caking agent that contains redox curing-type nonaqueous curable composition of claim 3, wherein, the 1st dose contains 0.1～50 weight part organo-peroxide (b) with respect to the liquid free radical polymerization monomers of 100 weight parts (a), the 2nd dose contains 0.1～50 weight part powdery, water-soluble reductibility compound (c) with respect to the liquid free radical polymerization monomers of 100 weight parts (a), and the 1st dose and the 2nd dose is subpackage in 1: 10～10: 1 with weight ratio.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004232731 | 2004-08-09 | ||
| JP232731/2004 | 2004-08-09 | ||
| PCT/JP2005/014502 WO2006016545A1 (en) | 2004-08-09 | 2005-08-08 | Redox curing-type nonaqueous curable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101001886A CN101001886A (en) | 2007-07-18 |
| CN101001886B true CN101001886B (en) | 2011-07-13 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800270207A Active CN101001886B (en) | 2004-08-09 | 2005-08-08 | Redox curing-type nonaqueous curable composition |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US8895680B2 (en) |
| EP (1) | EP1780223B1 (en) |
| JP (1) | JP4896724B2 (en) |
| KR (1) | KR20070052750A (en) |
| CN (1) | CN101001886B (en) |
| AT (1) | ATE475676T1 (en) |
| AU (1) | AU2005272477B2 (en) |
| CA (1) | CA2575820A1 (en) |
| DE (1) | DE602005022593D1 (en) |
| WO (1) | WO2006016545A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8329845B2 (en) * | 2007-01-23 | 2012-12-11 | Kuraray Noritake Dental Inc. | Divided redox-curing type composition |
| WO2008149929A1 (en) * | 2007-06-07 | 2008-12-11 | Tokuyama Dental Corporation | Dental filling/restoration kit |
| JP5379406B2 (en) * | 2007-06-07 | 2013-12-25 | 株式会社トクヤマデンタル | Dental filling and repair kit |
| ATE546127T1 (en) * | 2008-03-20 | 2012-03-15 | Ivoclar Vivadent Ag | POLYMER COATED GLASS FILLER FOR USE IN DENTAL MATERIALS |
| WO2010106903A1 (en) | 2009-03-18 | 2010-09-23 | クラレメディカル株式会社 | Redox-curing type composition |
| EP2233123B2 (en) † | 2009-03-24 | 2020-03-11 | Ivoclar Vivadent AG | Self-adhesive multi-component dental material |
| US9289359B2 (en) * | 2009-03-23 | 2016-03-22 | Ivoclar Vivadent Ag | Self-adhesive multicomponent dental material |
| JP4897124B2 (en) * | 2010-03-30 | 2012-03-14 | クラレメディカル株式会社 | Dental adhesive kit |
| DE102015103427A1 (en) | 2015-03-09 | 2016-09-15 | Kettenbach Gmbh & Co. Kg | Polymerizable dental material with phase transfer catalyst |
| DE102019106119A1 (en) | 2019-03-11 | 2020-09-17 | Kettenbach Gmbh & Co. Kg | Primer and kit consisting of primer and dental material |
| CN110368515B (en) * | 2019-08-12 | 2021-06-08 | 浙江派菲特新材料科技有限公司 | Preparation method of medical n-butyl ester adhesive with high bonding strength |
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| US4446246A (en) * | 1982-09-09 | 1984-05-01 | Three Bond Co., Ltd. | Catalyst systems for two-pack acrylic adhesive formulations |
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| JPS5339331A (en) | 1976-09-21 | 1978-04-11 | Kuraray Co Ltd | Adhesives for hard tissues of human bodies |
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| EP0061240A3 (en) * | 1981-03-20 | 1983-07-13 | Minnesota Mining And Manufacturing Company | Dentin and enamel adhesive |
| JPS5821687A (en) | 1981-07-29 | 1983-02-08 | Kuraray Co Ltd | (meth)acryloyloxyalkyl dihydrogenphosphate and its preparation |
| US4540722A (en) | 1982-01-15 | 1985-09-10 | Minnesota Mining And Manufacturing Company | Dentin and enamel adhesive |
| JPS59135272A (en) * | 1983-01-21 | 1984-08-03 | Kuraray Co Ltd | Adhesive |
| JPS61296077A (en) * | 1985-06-25 | 1986-12-26 | Three Bond Co Ltd | Electrically-conductive adhesive of two-pack contact curing type |
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2005
- 2005-08-08 EP EP05768904A patent/EP1780223B1/en active Active
- 2005-08-08 US US11/659,805 patent/US8895680B2/en active Active
- 2005-08-08 WO PCT/JP2005/014502 patent/WO2006016545A1/en active Application Filing
- 2005-08-08 CN CN2005800270207A patent/CN101001886B/en active Active
- 2005-08-08 DE DE602005022593T patent/DE602005022593D1/en active Active
- 2005-08-08 JP JP2006531617A patent/JP4896724B2/en active Active
- 2005-08-08 CA CA002575820A patent/CA2575820A1/en not_active Abandoned
- 2005-08-08 AU AU2005272477A patent/AU2005272477B2/en not_active Ceased
- 2005-08-08 KR KR1020077003093A patent/KR20070052750A/en not_active Application Discontinuation
- 2005-08-08 AT AT05768904T patent/ATE475676T1/en not_active IP Right Cessation
-
2010
- 2010-05-28 US US12/789,997 patent/US20100240798A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446246A (en) * | 1982-09-09 | 1984-05-01 | Three Bond Co., Ltd. | Catalyst systems for two-pack acrylic adhesive formulations |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1780223B1 (en) | 2010-07-28 |
| EP1780223A4 (en) | 2009-03-11 |
| JP4896724B2 (en) | 2012-03-14 |
| CA2575820A1 (en) | 2006-02-16 |
| AU2005272477A1 (en) | 2006-02-16 |
| AU2005272477B2 (en) | 2009-12-17 |
| DE602005022593D1 (en) | 2010-09-09 |
| CN101001886A (en) | 2007-07-18 |
| KR20070052750A (en) | 2007-05-22 |
| US20080081889A1 (en) | 2008-04-03 |
| EP1780223A1 (en) | 2007-05-02 |
| WO2006016545A1 (en) | 2006-02-16 |
| ATE475676T1 (en) | 2010-08-15 |
| US8895680B2 (en) | 2014-11-25 |
| US20100240798A1 (en) | 2010-09-23 |
| JPWO2006016545A1 (en) | 2008-05-01 |
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Address after: Okayama County, Japan Patentee after: Kuraray Noritake Dental Inc Address before: Okayama County, Japan Patentee before: Kuraray Medical Inc. |